U.S. patent number 3,819,536 [Application Number 05/318,339] was granted by the patent office on 1974-06-25 for process for preparing a catalyst based on ruthenium.
This patent grant is currently assigned to Ford Motor Company. Invention is credited to Ralph A. Dalla Betta, Haren S. Gandhi, Joseph T. Kummer, Mordecai Shelef.
United States Patent |
3,819,536 |
Dalla Betta , et
al. |
June 25, 1974 |
PROCESS FOR PREPARING A CATALYST BASED ON RUTHENIUM
Abstract
A process is taught for producing a ruthenium catalyst. A fixing
compound, selected from alkaline earth materials or rare earth
materials which decompose to an oxide of the material, is deposited
on a catalytic support. A hydrated, halogenated ruthenium compound
which reduces to ruthenium is also deposited on the catalytic
support. The materials on the support are heated in a reducing
atmosphere to form the ruthenium metal. After the reducing step the
materials are fixed by heating them to a ruthenate forming
temperature. The product produced in this manner is desirable for
use in the catalytic conversion, in a reducing atmosphere, of
oxides of nitrogen. The ruthenium catalyst of the product produced
by this method is resistant to volatilization when exposed to an
oxidizing ambient.
Inventors: |
Dalla Betta; Ralph A.
(Southfield, MI), Gandhi; Haren S. (Dearborn Heights,
MI), Kummer; Joseph T. (Ann Arbor, MI), Shelef;
Mordecai (Southfield, MI) |
Assignee: |
Ford Motor Company (Dearborn,
MI)
|
Family
ID: |
23237762 |
Appl.
No.: |
05/318,339 |
Filed: |
December 26, 1972 |
Current U.S.
Class: |
502/302; 423/212;
502/328; 502/332; 423/213.5 |
Current CPC
Class: |
B01J
23/63 (20130101); B01J 23/56 (20130101); B01J
23/58 (20130101); B01D 53/9413 (20130101); B01D
2255/2042 (20130101); B01D 2255/1026 (20130101) |
Current International
Class: |
B01J
23/54 (20060101); B01D 53/94 (20060101); B01J
23/56 (20060101); B01J 23/58 (20060101); B01j
011/08 () |
Field of
Search: |
;252/466PT,462,473,475,457,463,455R,477R ;423/212 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Wyman; Daniel E.
Assistant Examiner: Demers; A. P.
Attorney, Agent or Firm: Johnson; William E. Zerschling;
Keith L.
Claims
We claim:
1. A method of forming a ruthenium containing catalyst system in
which the activity of the catalytic material of the system is not
destroyed or severely reduced when the system is exposed to
oxidizing conditions of either a prolonged or a sporadic nature,
which method comprises the steps of:
coating a suitable catalytic support with a fixing compound
selected from the group consisting of alkaline earth materials and
rare earth materials, which compound upon decomposition produces an
oxide of the alkaline earth material or the rare earth
material;
coating said catalytic support with a hydrated, halogenated
ruthenium compound which produces ruthenium upon reduction;
reducing the ruthenium compound which has been applied to said
catalytic support to ruthenium; and
fixing the ruthenium with said fixing compound by heating said
catalytic support to a temperature sufficient to have said
compounds form a ruthenate.
2. The method of claim 1 wherein: said reducing step is carried out
in a hydrogen atomosphere at a temperature in the range of
200.degree.C to 800.degree.C for 1 hour to 20 hours.
3. The method of claim 1 wherein: said fixing step is carried out
at a temperature in the range of 800.degree.C to 1,000.degree.C for
10 minutes to 6 hours.
4. The method of claim 1 further including:
depositing of gamma alumina containing material on said catalytic
support;
drying said catalytic support; and
calcining said support all prior the deposition of said coatings on
said catalytic support.
5. The method of claim 1 wherein: said hydrated, halogenated
ruthenium compound is placed on said catalytic support prior to
said other material.
6. A method of forming a ruthenium containing catalyst system in
which the activity of the catalytic material of the system is not
destroyed or severely reduced when the system is exposed to
oxidizing conditions of either a prolonged or a sporadic nature,
which method comprises the steps of:
preparing a first solution of a fixing compound selected from the
group consisting of alkaline earth materials and rare earth
materials, which compound upon decomposition produces an oxide of
the alkaline earth material or the rare earth material;
soaking a catalytic support in said first solution;
drying said catalytic support;
calcining said catalytic support;
preparing a second solution of a hydrated, halogenated ruthenium
compound which produces ruthenium upon reduction;
soaking said catalytic support in said second solution;
drying said catalytic support;
reducing the ruthenium compound applied to said catalytic support;
and
fixing the ruthenium with said fixing compound by heating said
catalytic support to a temperature sufficient to have said
compounds form a ruthenate.
7. The method of claim 6 wherein: the order of soaking the
catalytic support in said two solutions is reversed.
8. The method of claim 6 wherein: said first solution has a
concentration in the range of 2.0 percent to 40 percent, and
wherein said soaking of said catalytic support is for a time from 5
minutes to 3 hours, whereby the concentration of said material from
said first solution on said catalytic support in the final article
will be in the range from 0.5 percent to 10 percent.
9. The method of claim 6 wherein: said second solution has a
concentration in the range of 0.04 percent to 8 percent, and
wherein said soaking of said catalytic support is for a time from 5
minutes to 3 hours, whereby the concentration of said ruthenium
compound on said catalytic support from said second solution will
produce a ruthenium metal concentration in the final article in the
range from 100 ppm to 20,000 ppm.
10. The method of claim 6 wherein: both drying steps take place at
a temperature in the range from 50.degree.C to 300.degree.C and for
a time in the range from 1 hour to 10 hours; and wherein said
calcining step take place at a temperature in the range from
400.degree.C to 800.degree.C and for a time in the range from 1
hour to 10 hours.
11. The method of claim 6 wherein: said reducing step is carried
out in a hydrogen atmosphere at a temperature in the range of
200.degree.C to 800.degree.C for 1 hour to 20 hours.
12. The method of claim 6 wherein: said fixing step is carried out
at a temperature in the range of 800.degree.C to 1,000.degree.C for
10 minutes to 6 hours.
Description
BACKGROUND OF THE INVENTION
U.S. Pat. application, Ser. No. 174,594, filed Aug. 25, 1971, now
abandoned, and assigned to the same assignee as the present
application, hereby incorporated by reference, teaches the use of
ruthenium as a catalyst for converting oxides of nitrogen in
combustion products of an engine into other compounds. In general,
this same application teaches that ruthenium, in a reducing
atmosphere, is effective to catalyze the reaction of oxides of
nitrogen into other compounds without the formation of ammonia.
In working with such a ruthenium catalyst, it has been discovered
that if such catalyst is exposed to an oxidizing ambient at high
temperatures, any ruthenium metal contained therein will
volatilize. Such oxidizing conditions are unavoidable in the
operation of an engine as an oxidizing condition will generally
occur upon a cold start of that engine or during some other mode of
driving. Thus a ruthenium metal catalyst will slowly volatilize
over the use of the engine and the conversion efficiency of a
catalyst system based on pure, unprotected, ruthenium metal will
decrease.
In view of such a decrease of efficiency, it is desirable to fix
somehow the ruthenium in such a catalyst system in a manner that it
will not volatilize when exposed to an oxidizing ambient. It is
desirable to fix the ruthenium in such a fashion that its exposure
to an oxidizing ambient will not adversely affect its ability to
convert subsequently any undesirable nitrogen compounds found in an
exhaust gas having reducing characteristics.
SUMMARY OF THE INVENTION
This invention relates to a method of forming a ruthenium
containing catalyst and the product produced thereby and, more
particularly, to such a method in which the ruthenium is fixed in
the catalytic system in such a manner that its effectiveness is not
destroyed or reduced by exposure of the system to an oxidizing
ambient.
In its broadest application, the method of this invention is
carried out by placing a fixing compound selected from the group
comprising alkaline earth materials and rare earth materials which
form oxides thereof upon decomposition on a catalytic support and
which also subsequently form ruthenates. Also deposited on the
catalytic support is a hydrated, halogenated ruthenium compound
which reduces to ruthenium. The compounds deposited on the
catalytic support are treated in a reducing atmosphere to reduce
the ruthenium compound. The catalytic support is then heated to a
temperature sufficient for the ruthenium to react with the fixing
compound to produce a ruthenate.
In greater detail, the method of this invention teaches that the
application of the compounds to the catalytic support may take
place by soaking a support in a solution of the compounds. The
order of application of the materials is semi-critical and it is
preferred to deposit the ruthenium metal last so that it is not
covered over and so that the reducing step may be effectively
carried out thereon. A preferred ruthenium compound is ruthenium
trichloride and in the final catalytic system the concentration of
ruthenium should be from at least 100 parts per million (ppm) to
20,000 ppm.
The product produced by this method is a ruthenium catalyst system
in which ruthenium is effective for catalyzing the reduction of
nitrogen oxide compounds to other compounds without any substantial
formation of ammonium. The catalyst system is also one which will
not volatilize or have its efficiency decreased substantially after
the system has been exposed to an oxidizing ambient.
The compounds used in the method of this invention may be deposited
on compatible type of a catalytic support known in the art. The
catalytic support may be pretreated with a selected material in
order to increase its effective surface area prior to the
deposition of the compounds in accordance with this invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In order to illustrate the method of this invention, a preferred
embodiment is described hereinbelow.
A 4 21/32 inch diameter by 3 inch long catalytic support produced
in the manner such as shown in Johnson, et al, U.S. Pat. No.
3,444,925 is selected which weights about 500 grams. The support is
coated with a slurry containing 15 percent by weight of "Dispal-M,"
a gamma alumina sold by Continental Oil Company. This material is a
hydrated alumina and is typical of the many materials which are
available of this type. The slurry is applied to the support in
order to increase its effective surface area for catalytic
deposition. The coated support is dried at 120.degree.C and
calcined at 600.degree.C. The above procedure is repeated,
generally two or three times, until about 10 percent by weight of
the support is the gamma alumina. The surface area of the support
at this point is about 14 square meters per gram.
The next step in the method taught herein is to coat the catalytic
support with a fixing compound selected from the group consisting
of alkaline earth materials and rare earth materials, which fixing
compound upon thermal decomposition will produce an oxide of the
alkaline earth material or the rare earth material which will
subsequently react with ruthenium to form a ruthenate. In this
specific example, the monolith or support is impregnated with a
solution containing Ba(NO.sub.3).sub.2. The 3 inch long support
weighing 500 grams picks up about 125 cc. of solution. In this
case, a solution containing 15 grams of barium as
Ba(NO.sub.3).sub.2 is used to impregnate the support. This will
result in 3 percent of the total weight of the support being
barium. The support is dried at 120.degree.C and calcined at
600.degree.C for 2 hours.
The next step in the overall method is to coat the catalytic
support with a hydrated, halogenated ruthenium compound which
produces ruthenium upon reduction. In this particular example, the
compound selected to accomplish this is a ruthenium trichloride.
Sufficient ruthenium trichloride is dissolved in water so that, in
this case, 2,000 ppm ruthenium is carried over onto the support.
After the catalytic support has been impregnated with the solution,
the support is dried at 120.degree.C.
The next step in the procedure is to subject the support on which
the two materials have been coated to a reducing atmosphere. In
this preferred embodiment, the reducing operation is carried out in
a hydrogen atmosphere at 400.degree.C to 450.degree.C for 4 hours.
This step results in a very finely dispersed ruthenium in close
proximity with barium oxide. The ruthenium metal on the catalyst
surface is then fixed, as a ruthenate, by heating the support to a
temperature in the range of 800.degree.C to 1,000.degree.C for 10
minutes to 6 hours.
It may be questioned that the barium oxide might react with the
gamma alumina but this has been checked and we have found that
barium oxide does not react at temperatures up to 1,300.degree.C
with gamma alumina in a dry system.
The catalyst system constructed as above described when tested on a
dynamometer, gave 100 percent NO.sub.x conversion efficiency at
850.degree.F and at space velocity equal to 70,000 hours
.sup.-.sup.1. The procedures of the above example may be repeated
utilizing various rare earth materials formed from such materials
as lanthanum, cerium, praseodymium, samarium, etc., or it may be
based on alkaline earth materials formed from strontium, calcium,
magnesium, and beryllium. While the ruthenium containing solution
was formed from ruthenium trichloride, other halogenated compounds
of ruthenium may be used or any other soluble salts.
The support described herein is only one of many types of supports
which are already known in the art. It is true that other catalytic
supports may be used in the method of this invention. In some
cases, because of the already extensive surface area of a
particular catalytic support, it is not necessary to increase the
surface area of the support by further treatment. A catalytic
support can also be in the form of pellets, beads or any small type
structures already known in the art.
As mentioned above, the major steps involved herein involve the
reducing of the ruthenium once it has been placed on the catalytic
support in order to develop ruthenium. Once the ruthenium metal is
developed, it is fixed in place by heating the support to a high
temperature for a set period of time. In this condition, the
ruthenium metal has an opportunity to react with the decomposed
stabilizing compound, namely an alkaline earth oxide or rare earth
oxide, to form a ruthenate. Once the ruthenate is formed, the
catalyst system is complete.
As an explanation of the theory by which the catalyst system of
this invention is operative, certain tests were carried out on the
materials employed herein and the following was discovered.
Thermo-gravimetric analysis show that ruthenates, for example
barium ruthenate, are stable towards volatilization under oxidizing
conditions up to 1,100.degree.C whereas ruthenium oxide powder
starts to volatilize at a slow rate even at temperatures as low as
400.degree. to 500.degree.C and at very fast rate when held at
1,100.degree.C under oxidizing conditions. When only ruthenium
oxide is employed in an oxidizing ambient, it takes only about 3
hours to lose 30 percent of the compound at 1,100.degree.C and a
space velocity equal to 600 hr .sup.-.sup.1 due to volatilization
compared with no loss at all in the case of a ruthenate such as
barium ruthenate. These tests are conducted on the pure material
and not on the material deposited on a catalytic support.
Further thermo-gravimetric studies on barium ruthenate showed that
barium ruthenate, when subjected to a stream of 6.5 percent CO and
the balance of nitrogen, loses weight at 450.degree.C. The sample
was held at 1,200.degree.C for an hour until it reached a steady
state weight. A portion of the sample was analyzed by x-ray
diffraction and was found to contain barium oxide and ruthenium
metal. The sample was then subjected to a stream of air at
1,200.degree.C whereby it regained some weight. The sample was
analyzed by x-ray diffraction and it was found to be pure barium
ruthenate. This testing was repeated on another sample of barium
ruthenate which was subjected to the reduction and oxidation cycle
at 1,200.degree.C. Each time after oxidation, the sample came back
to the exact initial weight. At the end of the sixth cycle, the
sample was analyzed by x-ray diffraction techniques and was
identified as pure barium ruthenate. Similar thermo-gravimetric
experiments were done on pure lanthanum ruthenate which was also
found to behave in a similar fashion. Lanthanum ruthenate reduces
under reducing conditions to lanthanum oxide and ruthenium and
under oxidizing conditions oxidizes to lanthanum ruthenate.
The explanation, therefore, of the mechanism of the ruthenium
catalyst system disclosed herein is believed to be as follows.
Under the reducing conditions wherein the ruthenium is employed to
reduce undesirable nitrogen compounds, the active catalytic
material on the catalyst substrate is finely divided ruthenium. The
ruthenium in its finely divided state is closely associated with an
adjacent zone of the stabilizing alkaline earth oxide or rare-earth
oxide. Thus during active catalytic operation, ruthenium is the
catalyst. However, when oxidizing conditions exist and the
ruthenium is subjected to an oxidizing ambient, the ruthenium metal
reunites with the stabilizing alkaline earth oxide or rare-earth
oxide to form a stable ruthenate. The ruthenate composition does
not volatilize. When the catalyst is once again subjected to a
reducing condition, the ruthenate compound once again reforms
ruthenium and the stabilizing oxide.
It should be mentioned at this point that since the conditions in
the exhaust do not usually reach these high temperatures, that the
catalyst in actual use may not behave in the clear cut manner
described. Under conditions of use, where such high temperatures
(1,200.degree.C) are not reached, the catalyst may be only
partially reduced to ruthenium metal or only the surface layer of
the ruthenate reduced to ruthenium metal or even just a decrease in
the nominal valance of the surface ruthenium atoms. Under oxidizing
conditions, these processes would be reversed.
In view of this disclosure, many modifications of this invention
will be apparent to those skilled in the art. It is intended that
all such modifications which fall within the true scope of this
invention be included within the terms of the appended claims.
* * * * *